KR101658172B1 - Supported hybrid metallocene catalyst and method for preparing of olefin based polymer using the same - Google Patents

Abstract

The present invention relates to a novel hybrid supported metallocene catalyst and a process for producing olefinic polymers using the same. The hybrid supported metallocene catalyst according to the present invention can be used in the production of an olefinic polymer, and is excellent in processability, mechanical properties and haze characteristics, and can produce an olefinic polymer having a high molecular weight and a broad molecular weight distribution.

Description

TECHNICAL FIELD [0001] The present invention relates to a metallocene catalyst and a method for producing the olefin polymer using the metallocene catalyst. [0002]

The present invention relates to a novel hybrid supported metallocene catalyst and a process for producing olefinic polymers using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad, The composition distribution is not uniform and there is a limit in securing desired physical properties.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Accordingly, there is a continuing need for a process for preparing an olefin polymer of desired properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

On the other hand, the linear low density polyethylene is a resin which is produced by copolymerizing ethylene and an alpha olefin at a low pressure using a polymerization catalyst, has a short molecular weight distribution and a short chain length and has no long chain branch. Linear low density polyethylene film has high tensile strength and elongation as well as general polyethylene characteristics, and has excellent tear strength and falling impact strength. Therefore, it is used for stretch film and overlap film which are difficult to apply low density polyethylene or high density polyethylene .

However, linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mostly prepared in a single gas phase reactor or a single loop slurry reactor, and productivity is high compared to the process using 1-octene comonomer. Due to limitations of catalyst technology and process technology, there is a problem that the physical properties are considerably weaker than when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability. Much effort has been made to improve these problems,

U.S. Patent No. 4,935,474 discloses a process for preparing polyethylene having a broad molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 discloses a process for producing polyethylene which is excellent in processability using a mixture of a monomer having good comonomer binding property and a monomer having no comonomer binding property and is particularly suitable for a film. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose that a polyethylene having at least two kinds of metal compounds is used as a metallocene-based catalyst and has a molecular weight distribution of at least two, and is used for films, blow molding, It is reported that it is applicable. However, these products have improved processability, but the dispersed state of the unit particles in molecular weight is not uniform, so that the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

Against this backdrop, there is a continuing need to produce better products with a balance between physical and processability, and further improvements are needed.

In order to solve the problems of the prior art, the present invention provides a hybrid supported metallocene catalyst capable of producing an olefin polymer having excellent processability and improved transparency and mechanical properties, and a process for producing an olefin polymer using the same I want to.

Accordingly,

A first metallocene compound represented by Formula 1 below;

A second metallocene compound comprising at least one compound selected from compounds represented by Chemical Formula 2 or 3;

A cocatalyst compound; And

There is provided a hybrid supported metallocene catalyst comprising a support.

[Chemical Formula 1]

(2)

(3)

The above Formulas 1 to 3 will be described in more detail below.

Also, the present invention provides a process for producing an olefin-based polymer comprising polymerizing an olefin-based monomer in the presence of the hybrid supported metallocene catalyst.

The hybrid supported metallocene catalysts according to the present invention can be used in the production of olefin polymers having a high molecular weight and a broad molecular weight distribution. Therefore, the olefin-based polymer produced using the mixed supported metallocene catalyst is excellent in processability, mechanical properties and transparency, and can be usefully used for films and the like.

Hereinafter, the present invention will be described in more detail.

The hybrid supported metallocene catalyst according to the present invention comprises: a first metallocene compound represented by the following general formula (1); A second metallocene compound comprising at least one compound selected from compounds represented by Chemical Formula 2 or 3; A cocatalyst compound; And a carrier.

[Chemical Formula 1]

In Formula 1,

R 1 to R 4, R 9 and R 1 'to R 4' are the same or different and each independently represents hydrogen, halogen, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 6 to C 20 aryl group, An aryl group, or an arylalkyl group of C7 to C20;

R5 to R8 are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group And at least two adjacent ones of R5 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring;

L1 is a linear or branched alkylene group of C1 to C10;

Wherein D1 is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, C2 to C20 alkenyl group, or C6 to C20 aryl group;

A 1 represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, An alkoxyalkyl group of C20, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

M1 is a Group 4 transition metal;

X1 and X2 are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, To C20 alkoxy groups, or C1 to C20 sulfonate groups;

(2)

In Formula 2,

R10 to R13 and R10 'to R13' are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, Or an aryl group of C1 to C20 or an amine group of C1 to C20, and at least two of R10 to R13 and R10 'to R13' are connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring Can be;

Z1 and Z2 are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C6 to C10 aryloxy group, A C2 to C20 alkenyl group, a C7 to C40 alkylaryl group, or a C7 to C40 arylalkyl group;

Q is a C1 to C20 alkylene group, a C3 to C20 cycloalkylene group, a C6 to C20 arylene group, a C7 to C40 alkylarylene group, or a C7 to C40 arylalkylene group;

M2 is a Group 4 transition metal;

X3 and X4 are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, To C20 alkoxy groups, or C1 to C20 sulfonate groups;

 (3)

In Formula 3,

M3 is a Group 4 transition metal;

X5 and X6 are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, To C20 alkoxy groups, or C1 to C20 sulfonate groups;

R14 to R19 are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, C20 alkylsilyl, C6-C20 arylsilyl or C1-C20 amine group, and two or more adjacent R14 through R17 are connected to each other to form one or more aliphatic rings , An aromatic ring, or a heterocyclic ring;

L2 is a straight or branched alkylene group of C1 to C10;

D2 is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, C2 to C20 alkenyl group, or C6 to C20 aryl group;

A halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, An alkoxyalkyl group of C20, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

B is a carbon, silicon, or germanium bridge linking a cyclopentadienyl ligand and JR 19 _{z -y} by a covalent bond;

J is a Group 15 element or a Group 16 element of the periodic table;

z is the oxidation number of the element J;

y is the combined number of J elements.

In the metallocene compounds according to the present invention, the substituents of the above formulas (1) to (3) will be described in more detail as follows.

Examples of the C1 to C20 alkyl group include a linear or branched alkyl group and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, An octyl group, and the like, but are not limited thereto.

The C2 to C20 alkenyl group includes a straight chain or branched alkenyl group, and specific examples include, but are not limited to, an allyl group, an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group.

The C6 to C20 aryl group includes an aryl group of a monocyclic or condensed ring, and specifically includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group and a fluorenyl group.

The C5 to C20 heteroaryl group includes a heteroaryl group of a monocyclic or condensed ring and includes a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.

Examples of the C1 to C20 alkoxy groups include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.

Examples of the Group 4 transition metal include, but are not limited to, titanium, zirconium, and hafnium.

In the mixed supported metallocene catalyst according to the present invention, R1 to R9 and R1 'to R8' in the above formula (1) each independently represents a hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, A butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a phenyl group, but is not limited thereto.

In the mixed supported metallocene catalyst according to the present invention, it is more preferable that L 1 in the above formula (1) is a linear or branched alkylene group of C 4 to C 8, but is not limited thereto. The alkylene group may be substituted or unsubstituted with a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group.

In the mixed supported metallocene catalyst according to the present invention, A1 in the formula (1) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n- butyl group, a tert- butyl group, a methoxymethyl group, More preferably a methyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but is not limited thereto.

In the mixed supported metallocene catalyst according to the present invention, Q in the formula (2) is an alkylene group of C1 to C20, Z1 and Z2 are each independently hydrogen, a C1 to C20 alkyl group or a C1 to C20 alkoxy group, X3 and X4 may be halogen, but are not limited thereto.

In the hybrid supported metallocene catalyst according to the present invention, L2 in the above formula (3) is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto. The alkylene group may be substituted or unsubstituted with a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group.

In the hybrid supported metallocene catalyst according to the present invention, A2 in the above formula (3) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n- butyl group, a tert-butyl group, a methoxymethyl group, More preferably a methyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but is not limited thereto.

In Formula 3, B is silicon and J is nitrogen, but it is not limited thereto.

R14 to R19 in Formula 3 may each independently be hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C1 to C20 alkoxy group, but is not limited thereto.

The method for producing the metallocene compound represented by the above Chemical Formulas 1 to 3 is described in the following Examples.

The first metallocene compound of Formula 1 forms a structure in which a fluorene derivative is bridged by a bridge and has a non-covalent electron pair capable of acting as a Lewis base in the ligand structure, thereby forming a surface having Lewis acid properties And exhibits high polymerization activity even when supported. In addition, since the electron-rich fluorene group is contained, the olefin-based polymer having high molecular weight can be polymerized with high activity.

The hybrid supported metallocene catalyst according to the present invention comprises at least one first metallocene compound represented by Formula 1 and at least one second metallocene compound selected from the compounds represented by Formula 2 or 3 And more than two species are mixed and supported on a carrier together with a promoter compound.

The first metallocene compound represented by Formula 1 of the hybrid supported metallocene catalyst contributes mainly to the formation of a high molecular weight copolymer and the second metallocene compound represented by Formula 2 is a copolymer of relatively low molecular weight . In addition, the second metallocene compound represented by the formula (3) can contribute to the production of a medium molecular weight copolymer. Therefore, when a mixed supported metallocene catalyst containing three metallocene compounds including the metallocene compounds of the above Chemical Formulas 1 to 3 is used, the miscibility of the high molecular weight and low molecular weight copolymers is low, Can be complemented to have a broad molecular weight distribution, thereby improving workability and exhibiting high transparency.

According to an embodiment of the present invention, the hybrid supported metallocene catalyst may include at least one first metallocene compound represented by the general formula (1) and at least one second metallocene compound represented by the general formula (2).

According to another embodiment of the present invention, the hybrid supported metallocene catalyst comprises at least one first metallocene compound represented by the general formula (1) and at least one second metallocene compound represented by the general formula (2) And at least one second metallocene compound.

Therefore, in the hybrid supported metallocene catalyst of the present invention, the first metallocene compound represented by the formula (1) and the second metallocene compound selected from the compounds represented by the formula (2) or (3) Of at least two or more kinds of metallocene compounds, preferably three kinds of metallocene compounds of different kinds. As a result, the compatibility of the high-molecular-weight and low-molecular-weight copolymers can be complemented to produce olefin polymers having high molecular weight olefin-based copolymers and simultaneously having excellent molecular weight distribution and excellent processability.

In the mixed supported metallocene catalyst according to the present invention, the co-catalyst to be supported on the support for activating the metallocene compound is an organometallic compound containing a Group 13 metal, And is not particularly limited as long as it can be used in polymerization.

Specifically, the promoter compound may include at least one of the promoter compounds represented by the following formulas (4) to (6).

[Chemical Formula 4]

- [Al (R20) -O] _n -

In Formula 4,

R20 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more;

[Chemical Formula 5]

D (R20) ₃

In Formula 5,

R20 is as defined in Formula 4 above;

D is aluminum or boron;

[Chemical Formula 6]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 6,

L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same or different from each other and each independently represents a C6 to C20 aryl group or a C1 to C20 alkyl group in which at least one hydrogen atom is substituted with halogen, C1 to C20 hydrocarbon, alkoxy or phenoxy.

Examples of the compound represented by the general formula (4) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra -Phenyl) boron and the like, triphenylamine car I Titanium tetra-penta flow phenylboronic.

In the mixed supported metallocene catalyst according to the present invention, the mass ratio of the transition metal to the support of the first and second metallocene compounds is preferably 1: 1 to 1: 1,000. When the carrier and the metallocene compound are contained at the above mass ratio, they exhibit appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In addition, the mass ratio of the co-catalyst compound to the support is preferably 1:20 to 20: 1, and the mass ratio of the co-catalyst compound to the support is preferably 1:10 to 100: 1.

The mass ratio of the first metallocene compound to the second metallocene compound is preferably 1: 100 to 100: 1. When the cocatalyst and the metallocene compound are contained in the above mass ratio, they exhibit appropriate catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In the hybrid supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on the surface thereof can be used as the carrier, and preferably, a hydroxy group and a siloxane group having high reactivity, You can use your carrier.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 100 to 800 ° C. When the drying temperature of the carrier is less than 100 ° C., the moisture is too much to react with the cocatalyst on the surface. When the temperature exceeds 800 ° C., the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

The hybrid supported metallocene catalyst according to the present invention is characterized in that it comprises a step of supporting a promoter compound on a support, supporting the first metallocene compound on the support, and supporting the second metallocene compound on the support . ≪ / RTI > In the method for preparing the hybrid supported metallocene catalyst, the order of the step of supporting the first and second metallocene compounds may be changed as necessary. That is, a first metallocene compound is first supported on a carrier, and then a second metallocene compound is further supported to prepare a hybrid supported metallocene catalyst, or a second metallocene compound is first supported on a carrier , The first metallocene compound may be supported thereon. Alternatively, the first and second metallocene compounds may be simultaneously introduced and carried.

In the preparation of the hybrid supported metallocene catalyst, a hydrocarbon solvent such as pentane, hexane, heptane or the like or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent. In addition, the metallocene compound and the co-catalyst compound may be used in the form supported on silica or alumina.

According to another aspect of the present invention, there is provided a process for producing an olefin-based polymer comprising polymerizing an olefin-based monomer in the presence of the hybrid supported metallocene catalyst.

In the process for preparing an olefin polymer according to the present invention, specific examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene and the like.

The olefin-based polymer is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.

In the case where the olefin-based polymer is an ethylene / alpha olefin copolymer, the content of the alpha-olefin as the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose and the like of the olefin-based polymer. More specifically, it may be more than 0 and 99 mol% or less.

The polymerization reaction can be homopolymerized with one olefin monomer or copolymerized with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The mixed supported metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, A hydrocarbon solvent substituted with the same chlorine atom, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

An olefin-based copolymer having a molecular weight distribution curve of not less than 2 can be prepared using the hybrid supported metallocene catalyst. When the mixed metallocene catalyst is used, an olefin polymer having a relatively high molecular weight can be produced by the first metallocene compound, and a relatively low molecular weight olefin polymer Based polymer can be produced. In particular, the mixed supported metallocene catalyst may contain at least one first metallocene compound of Formula 1, at least one second metallocene compound of Formula 2, and at least one second metallocene compound of Formula 3 , An olefin polymer having a high molecular weight, a low molecular weight and a medium molecular weight is produced, and an olefin polymer exhibiting improved transparency can be prepared by improving the compatibility between a high molecular weight polymer and a low molecular weight polymer while having a broad molecular weight distribution.

With the hybrid supported metallocene catalyst of the present invention, the polymerization temperature may be from about 25 to about 500 캜, preferably from about 25 to about 200 캜, more preferably from about 50 to about 150 캜. In addition, the polymerization pressure may be from about 1 to about 100 Kgf / cm ² , preferably from about 1 to about 70 Kgf / cm ² , more preferably from about 5 to about 50 Kgf / cm ² .

The olefinic polymer according to the present invention can be obtained by homopolymerization of ethylene or copolymerization of ethylene with an alpha olefin using the hybrid supported metallocene compound as a catalyst, and may have this or a molecular weight distribution.

The hybrid supported metallocene catalyst of the present invention exhibits excellent activity, and when the olefin polymer is prepared using the mixed supported metallocene catalyst of the present invention, a polymer having a high molecular weight and a broad molecular weight distribution can be produced, The olefin-based polymer has excellent effects on physical properties and processability.

For example, the olefinic polymers prepared by the process of the present invention exhibit a high molecular weight distribution (Mw / Mn, PDI) of from about 1.0 to about 15, preferably from about 2.5 to about 7,

In the present invention, the weight average molecular weight (Mw) of the olefin-based polymer may be about 10,000 to about 500,000 g / mol, and preferably about 50,000 to about 300,000 g / mol, but is not limited thereto.

Therefore, the olefin-based polymer produced by the production method of the present invention is excellent in mechanical properties such as tensile strength, tear strength and the like, processability, haze, etc., and can be applied variously according to the application, A film can be provided.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

< Example >

< Metallocene  Preparation of compounds Example >

Manufacturing example  1: 1st Metallocene  Preparation of compounds

( tert - This -O- ( CH ₂ ) ₆ ) MeSi (9- C ₁₃ H ₉ ) ₂ ZrCl ₂ Manufacturing

1) Preparation of ligand compound

Bu-O- (CH ₂ ) ₆ MgCl ₂ solution as a Grignard reagent was obtained from the reaction between tert-Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The obtained Grignard compound was added to a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at -30 ° C, stirred at room temperature for 8 hours or longer, dried _{tert-Bu-O- (CH 2} ) 6 to obtain a compound of SiMeCl ₂ (92% yield).

Fluorene (3.33 g, 20 mmol), hexane (100 mL) and MTBE (1.2 mL, 10 mmol) were added to the reactor at -20 ° C and 8 mL of n-BuLi (2.5 M in Hexane ) Was added slowly, and the mixture was stirred at room temperature for 6 hours. After the stirring was completed, the reactor temperature was cooled to -30 ° C and a solution of tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (2.7 g, 10 mmol) dissolved in hexane (100 ml) The prepared fluorenyl lithium solution was slowly added over 1 hour. The mixture was stirred at room temperature for 8 hours or more and then extracted with water and evaporated to obtain tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₁₀ ) ₂ compound (5.3 g , Yield: 100%). The structure of the ligand was confirmed by &lt; 1 &gt; H-NMR.

_{1H NMR (500MHz, CDCl 3)} : -0.35 (MeSi, 3H, s), 0.26 (Si-CH 2, 2H, m), 0.58 (CH 2, 2H, m), 0.95 (CH 2, 4H, m) , 1.17 (tert-BuO, 9H , s), 1.29 (CH 2, 2H, m), 3.21 (tert-BuO-CH 2, 2H, t), 4.10 (Flu-9H, 2H, s), 7.25 (Flu -H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

2) Preparation of metallocene compound

To a solution of (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₁₀ ) ₂ (3.18 g, 6 mmol) / MTBE (20 mL) at -20 ° C., 4.8 ml of n-BuLi M in hexane) was slowly added to the reaction mixture and the mixture was allowed to react for at least 8 hours while rising to room temperature. Then, the dilithium salts slurry solution prepared above was reacted with ZrCl ₄ (THF) ₂ (2.26 g, 6 mmol) (20 mL), and further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to obtain a red solid (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ ZrCl ₂ compound (4.3 g, yield 94.5% ).

1H NMR (500MHz, C6D6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH 2, 2H, m), 1.66 (CH 2, 4H, m), _{1.91 (CH 2, 4H, m} ), 3.32 (tert-BuO-CH 2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15 (Flu- H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64

Manufacturing example  2: 1st Metallocene  Preparation of compounds

( tert - This -O- ( CH ₂ ) ₆ ) MeSi ( C ₅ H ₄ ) (9- C ₁₃ H ₉ ) ZrCl ₂ Manufacturing

1) Preparation of ligand

Bu-O- (CH ₂ ) ₆ MgCl ₂ solution as a Grignard reagent from the reaction between tert-Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The prepared Grignard compound was stirred at room temperature for 8 hours or longer, and the filtered solution was vacuum-dried to obtain a solution of the Grignard compound in a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (yield 92%).

To the reactor was added fluorene (100 g, 0.60 mol), hexane (4.5 L) and MTBE (35.7 mL, 0.3 mol), and an equivalent amount of n-BuLi (2.5 M in Hexane) After stirring at room temperature for 6 hours, the mixture was stirred for 3 hours or more at 40 DEG C. After the completion of the stirring, the reactor was cooled to -30 DEG C, and tert-Bu -O- (CH ₂ ) ₆ SiMeCl ₂ (162.8 g, 0.6 mol) was slowly added over 1 hour to the solution of fluorenyl lithium prepared above. After stirring at room temperature for more than 8 hours, it was further cooled to -30 ° C and reacted with C ₅ H ₅ Na (55.9 g, 0.6 mol) / THF (4 L) for 6 hours or longer. Dried and extracted with hexane to give the (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₅ H ₅ ) (9-C ₁₃ H ₁₀ ) compound as a yellow ligand (yield 99% overall yield 91%). The structure of the ligand was confirmed by &lt; 1 &gt; H-NMR.

_{1H NMR (400MHz, CDCl 3)} : -0.13, 0.06 (MeSi, 3H, s), 0.27, 0.35 (Si-CH 2, 2H, m), 1.19 (tert-BuO, 9H, s), 1.15-1.40 ( _{CH 2, 4H, m),} 1.41-1.55 (CH 2, 4H, m), 2.70, 3.10 (methylene CpH, 2H, brs), 3.31 (tert-BuO-CH 2, 2H, t), 4.01 (methylene Flu (Flu-H, 1H, s), 6.00-6.30, 6.40-6.70 (CpH, 4H, m), 7.26-7.50 (Flu-H, 1H, d), 7.80 (Flu-H,

2) Preparation of metallocene compound

To a solution of (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₅ H ₅ ) (9-C ₁₃ H ₁₀ ) (310.1 g, 0.72 mol) / toluene (3.0 L) at -30 ° C was added 2 equivalents The slurry solution of ZrCl ₄ (THF) ₂ (271.7 g, 0.72 mol) / toluene (2.5 L) was added dropwise at -30 ° C to the reaction mixture at room temperature for 8 hours or longer while slowly adding n-BuLi (2.5 M in Hexane) The dilithium salts slurry solution prepared above was slowly added thereto, and further reacted at room temperature for 8 hours. All the volatile materials were vacuum dried, and a dichloromethane solvent was added to the oily liquid material to be filtered out. The filtered solution was vacuum dried, and hexane was added to induce a precipitate. The resulting precipitate was washed several times with hexane to obtain racemic (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ compound in the form of a red solid Yield 70%).

_{1H NMR (400MHz, C 6 D} 6): 0.66 (MeSi, 3H, s), 1.16 (tert-BuO, 9H, s), 1.35 (Si-CH 2, 2H, m), 1.40-1.75 (CH 2, 8H, m), 2.70, 3.30 (tert-BuO-CH 2, 2H, t), 5.46 (CpH, 2H, br d), 6.46 (CpH, 2H, br s), 7.05-7.20 (Flu-H, 2H , m), 7.34 (Flu-H, 1 H, d), 7.39 (Flu-H,

Manufacturing example  3: 2nd Metallocene  Preparation of compounds

J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. 1, 2-ethylene bis (indenyl) ZrCl ₂ compound was synthesized as disclosed in US Pat.

Manufacturing example  4: 2nd Metallocene  Preparation of compounds

tBu -O- ( CH ₂ ) ₆ ) ( CH ₃ ) Si ( C ₅ ( CH ₃ ) ₄ ) ( tBu -N) TiCl ₂  of  Produce

At room temperature, 50 g of Mg (s) was added to the 10 L reactor and 300 mL of THF was added. About 0.5 g of I ₂ was added, and the reactor temperature was maintained at 50 ° C. After the reactor temperature stabilized, 250 g of 6-t-buthoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. The addition of 6-t-butoxyhexyl chloride increased the reactor temperature by about 4 to 5 ° C. Followed by stirring for 12 hours while continuously adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. 2 mL of the resulting black solution was taken, and water was added to obtain an organic layer. 6-t-buthoxyhexane was confirmed by 1H-NMR. From the 6-t-butoxyhexane, the Gringanrd reaction proceeded well. Thus, 6-t-buthoxyhexyl magnesium chloride was synthesized.

500 g of MeSiCl ₃ and 1 L of THF were added to the reactor and the reactor temperature was cooled to -20 ° C. 560 g of synthesized 6-t-butoxyhexylmagnesium chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. After feeding of the Grignard reagent, the temperature of the reactor was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, it was confirmed that MgCl ₂ salt of white was formed. 4 L of hexane was added to remove the salt through a labdori to obtain a filter solution. The obtained filter solution was added to the reactor, and hexane was removed at 70 ° C to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t-butoxy hexyl) dichlorosilane compound through 1 H-NMR.

_{1H-NMR (CDCl 3):} 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

After 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, the reactor temperature was cooled to -20 占 폚. n-BuLi 480 mL feed pump at a rate of 5 mL / min. After the addition of n-BuLi, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, an equivalent amount of methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. After the reactor temperature was slowly raised to room temperature, the mixture was stirred for 12 hours. After the reactor was cooled to 0 ° C, 2 equivalents of t-BuNH ₂ was added. The reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of the reaction, THF was removed and 4 L of hexane was added to obtain a filter solution from which the salt was removed through a lapdry. After the filter solution was added to the reactor again, hexane was removed at 70 캜 to obtain a yellow solution. The obtained yellow solution was confirmed to be methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound through 1 H-NMR to obtain methyl (6-t-butoxyhexyl) (tetramethyl CpH) .

TiCl ₃ (THF) ₃ (10 mmol) was added to the dilithium salt of the ligand synthesized from n-BuLi and the ligand dimethyl (tetramethyl CpH) t-butylamine silane (dimethyl (tetramethylCpH) t- ). The reaction solution was agitated for 12 hours while slowly raising the temperature to -78 ° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution with a blue color was obtained. THF was removed from the resulting reaction solution, and hexane was added to filter the product. After removing the hexane solution obtained from the filter, desired from the 1H-NMR of _{(tBu-O- (CH 2)} ([methyl (6-t-buthoxyhexyl) silyl (η5-tetramethylCp) (t-Butylamido)] TiCl 2) 6 ) it was identified as _{(CH 3) Si (C 5} (CH 3) 4) (tBu-N) TiCl 2.

_{1H-NMR (CDCl 3):} 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 ~ 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3H)

&Lt; Preparation of hybrid supported catalyst Example >

Example  One

3.0 L of toluene solution was added to 20 L of high pressure reactor, 1,000 g of silica (SP2410, manufactured by Grace Davison) was added, and the reactor temperature was raised to 40 캜 while stirring. After the silica was sufficiently dispersed for 60 minutes, 5.4 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added, the temperature was raised to 60 ° C, and the mixture was stirred at 200 rpm for 12 hours. The temperature of the reactor was lowered to 40 ° C., stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decanted. After 3.0 kg of toluene was added and stirred for 10 minutes, the stirring was stopped, settling for 30 minutes and decanting the toluene solution.

2.0 kg of toluene was added to the reactor, 13.7 g of the metallocene compound of Preparation Example 1 and 1,000 mL of toluene were placed in the flask and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution prepared in Preparation Example 1 was charged into the reactor and stirred at 200 rpm for 90 minutes. Stirring was stopped and settling was performed for 30 minutes, and then the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, and 21.0 g of the metallocene compound of Preparation Example 3 and 1,000 mL of toluene were placed in a flask and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution of Preparation Example 3 thus prepared was charged into the reactor and stirred at 200 rpm for 90 minutes. Stirring was stopped and settling was performed for 30 minutes, and then the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, 15.2 g of the metallocene compound of Preparation Example 4 and 300 mL of toluene were placed in a flask and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution prepared in Preparation Example 4 was charged into the reactor and stirred at 200 rpm for 90 minutes. After the temperature of the reactor was lowered to room temperature, stirring was stopped, and the reaction solution was decanted by settling for 30 minutes.

After 2.0 kg of toluene was added and stirred for 10 minutes, stirring was stopped, settling for 30 minutes and decanting the toluene solution.

The reactor was charged with 3.0 kg of hexane, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. Followed by drying under reduced pressure at 50 캜 for 4 hours to prepare an 830 g-SiO ₂ hybrid supported catalyst.

Example  2

2.0 L of a toluene solution was added to 20 L of high pressure reactor, 1,200 g of silica (SP2412 manufactured by Grace Davison) was added, and the reactor was stirred while raising the temperature of the reactor to 40 캜. After silica was sufficiently dispersed for 60 minutes, 7.5 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added, the temperature was raised to 80 ° C, and the mixture was stirred at 200 rpm for 12 hours. The temperature of the reactor was lowered to 40 ° C, stirring was stopped, and the reaction solution was settled for 60 minutes before decanting the reaction solution. After 3.0 kg of toluene was added and stirred for 10 minutes, stirring was stopped, settling for 60 minutes and decanting the toluene solution.

2.0 kg of toluene was added to the reactor, and 33.2 g of the metallocene compound of Preparation Example 1 and 1,500 mL of toluene were added to the flask to prepare a solution, followed by sonication for 30 minutes. The metallocene compound / toluene solution prepared in Preparation Example 1 was charged into the reactor and stirred at 200 rpm for 90 minutes. Stirring was stopped, settling was performed for 60 minutes, and the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, 50.7 g of the metallocene compound of Preparation Example 3 and 1,500 mL of toluene were placed in a large volume of the flask, and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution of Preparation Example 3 thus prepared was charged into the reactor and stirred at 200 rpm for 90 minutes. Stirring was stopped, settling was performed for 60 minutes, and the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, and 36.7 g of the metallocene compound of Preparation Example 4 and 500 mL of toluene were added to the flask to prepare a solution, followed by sonication for 30 minutes. The metallocene compound / toluene solution prepared in Preparation Example 4 was charged into the reactor and stirred at 200 rpm for 90 minutes. After the reactor temperature was lowered to room temperature, the stirring was stopped, and the reaction solution was settled for 60 minutes, and then the reaction solution was decanted.

The reactor was charged with 2.0 kg of toluene and stirred for 10 minutes, then the stirring was stopped, settling for 60 minutes and decanting the toluene solution.

The reactor was charged with 3.0 kg of hexane, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. And dried under reduced pressure at 50 캜 for 4 hours to prepare a 1,130 g-SiO ₂ hybrid supported catalyst.

Example  3

3.0 L of a toluene solution was added to a 20 L sus high-pressure reactor, 1,000 g of silica (SP952X manufactured by Grace Davison, 200 ° calcination) was added, and the reactor was stirred while raising the temperature of the reactor to 40 ° C. After the silica was sufficiently dispersed for 60 minutes, 6.0 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added, the temperature was raised to 60 ° C, and the mixture was stirred at 200 rpm for 12 hours. The temperature of the reactor was lowered to 40 ° C., stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decanted. After 3.0 kg of toluene was added and stirred for 10 minutes, the stirring was stopped, settling for 30 minutes and decanting the toluene solution.

2.0 kg of toluene was added to the reactor, and 17.3 g of the metallocene compound of Preparation Example 1 and 1,000 mL of toluene were placed in a flask and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution prepared in Preparation Example 1 was charged into the reactor and stirred at 200 rpm for 90 minutes. Stirring was stopped and settling was performed for 30 minutes, and then the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, 31.1 g of the metallocene compound of Preparation Example 3 and 1,500 mL of toluene were placed in a large amount of the flask, and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution of Preparation Example 3 thus prepared was charged into the reactor and stirred at 200 rpm for 90 minutes. After the temperature of the reactor was lowered to room temperature, stirring was stopped, and the reaction solution was decanted by settling for 30 minutes.

After 2.0 kg of toluene was added and stirred for 10 minutes, stirring was stopped, settling for 30 minutes and decanting the toluene solution.

The reactor was charged with 3.0 kg of hexane, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. And dried under reduced pressure at 50 캜 for 4 hours to prepare a 700 g-SiO ₂ hybrid supported catalyst.

Example  4

3.0 L of toluene solution was added to 20 L of high pressure reactor, 1,000 g of silica (SP2410, manufactured by Grace Davison) was added, and the reactor temperature was raised to 40 캜 while stirring. After the silica was sufficiently dispersed for 60 minutes, 5.4 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added, the temperature was raised to 60 ° C, and the mixture was stirred at 200 rpm for 12 hours. The temperature of the reactor was lowered to 40 ° C., stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decanted. After 3.0 kg of toluene was added and stirred for 10 minutes, the stirring was stopped, settling for 30 minutes and decanting the toluene solution.

2.0 kg of toluene was added to the reactor, and 22.3 g of the metallocene compound of Preparation Example 2 and 1,000 mL of toluene were added to the flask to prepare a solution, followed by sonication for 30 minutes. The thus prepared metallocene compound / toluene solution of Preparation Example 2 was charged into the reactor and stirred at 200 rpm for 120 minutes. Stirring was stopped and settling was performed for 30 minutes, and then the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, 25.0 g of the metallocene compound of Preparation Example 3 and 1,500 mL of toluene were placed in a large volume of the flask, and the solution was prepared and subjected to sonication for 30 minutes. The metallocene compound / toluene solution of Preparation Example 3 thus prepared was charged into the reactor and stirred at 200 rpm for 90 minutes. After the temperature of the reactor was lowered to room temperature, stirring was stopped, and the reaction solution was decanted by settling for 30 minutes.

After 2.0 kg of toluene was added and stirred for 10 minutes, stirring was stopped, settling for 30 minutes and decanting the toluene solution.

The reactor was charged with 3.0 kg of hexane, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. And dried under reduced pressure at 50 캜 for 4 hours to prepare a 700 g-SiO ₂ hybrid supported catalyst.

&Lt; Olefin polymerization Example >

Example  5

The olefin polymer was prepared by charging the mixed supported metallocene catalyst obtained in Example 1 in an isobutane slurry loop process continuous polymerization reactor (reactor volume: 140 L, reaction flow rate: 7 m / s). 1-hexene was used as the comonomer, the reactor pressure was maintained at 40 bar, and the polymerization temperature was maintained at 88 占 폚.

Example  6 to 8

An olefin polymer was prepared in the same manner as in Example 5, except that the hybrid supported metallocene catalysts of Examples 2 to 4 were used, respectively.

Comparative Example  One

LUCENE ( ^TM) SP330 product of LG Chem, a commercial mLLDPE produced by the slurry loop process polymerization process, was prepared.

Comparative Example  2

LUPURE ^占 BB120 product of LG Chemical, a commercial HD-LDPE produced by radical reaction in a high pressure process, was prepared.

The polymerization conditions of Examples 5 to 8 are summarized in Table 1 below.

Example 5 Example 6 Example 7 Example 8 Catalyst used Example 1
(Production Example 1 /
Production Example 3 /
Production Example 4) Example 2
(Production Example 1 /
Production Example 3
Production Example 4) Example 3
(Production Example 1 /
Production Example 3) Example 4
(Production Example 2 /
Production Example 3) Ethylene feed
(kg / hr) 24 29 25 27 Hydrogen input (ppm) 190 135 186 135 1-Hexene input (mol%) 6.5 6.5 6.4 6.5 Slurry density (g / L) 550 545 550 554 Catalytic activity (kg PE / kg cat./hr) 2.6 5.1 4.2 3.6 Bulk density
(g / mL) 0.47 0.47 0.47 0.47 Settling efficiency (%) 62 63 61 59

< Experimental Example >

Production of film

The olefin polymers of Examples 5 to 8 and Comparative Examples 1 and 2 were melt-kneaded in an extruder (W & P Twin Screw Extruder, 75 psi, L / D = 36) Lt; RTI ID = 0.0 &gt; 210 C. &lt; / RTI &gt; The film was inflated using a single screw extruder (Xinhua Industrial Single Screw Extruder, Blown Film M / C, 50 psi, L / D = 20) at an extrusion temperature of 165 to 200 ° C to a thickness of 0.05 mm. At this time, the die gap was 2.0 mm and the blown-up ratio was 2.3.

Evaluation of physical properties of polymer and film

The physical properties and film properties of the olefin polymers of Examples 5 to 8 and Comparative Examples 1 and 2 were measured according to the following evaluation methods, and the results are shown in Table 2 and Table 3, respectively.

1) Density: ASTM 1505

2) Melt Index (MI, 2.16 kg / 10 kg): Measuring temperature 190 占 폚, ASTM 1238

3) MFRR (MFR ₁₀ / MFR ₂ ): MFR _{10 The} ratio of the melt index (MI, 10 kg load) divided by MFR ₂ (MI, 2.16 kg load).

4) Molecular weight, molecular weight distribution: Number-average molecular weight, weight-average molecular weight and Z-average molecular weight were measured using Gel Permeation Chromatography-FT-IR (GPC-FTIR) at a measurement temperature of 160 ° C. The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

5) Tensile strength at break, elongation at break: measured according to ASTM D 882. At this time, the test speed was 500 mm / min, and the average value was measured 10 times per one specimen.

6) Elmedorf tear strength: A film of a certain thickness was cut out in the form of a test piece with a die cutter and measured according to ASTM D 1922. At this time, the test speed was 500 mm / min, and the average value was measured 10 times per one specimen.

7) Dart impact: The drop impact strength was measured by measuring 20 times or more per film based on ASTM D 1709 [Method A].

8) Cloudiness: measured according to ASTM D 1003. At this time, the average value was measured 10 times per one specimen.

Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 density
(g / cm ³⁾ 0.925 0.826 0.926 0.926 0.929 0.925 The melt index (MI, 2.16 kg / 10 kg) 0.51 / 5.7 0.42 / 4.3 0.50 / 5.45 0.50 / 7.2 0.62 / 4.5 0.29 / 4.9 MFRR 11.2 10.1 11.5 14.5 7.3 16.9 Molecular Weight
(* 10 ⁴ g / mol) 12.8 12.6 12.8 16.2 13.1 10.6 Molecular weight distribution 5.9 5.1 5.5 8.3 3.0 4.6

Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Thickness (㎛) 52 48 48 52 50 48 Haze 20 17 31 42 12 12 Fallen impact strength
(g) 267 253 267 240 743 90 The tensile strength
(Kgf / cm ² ) MD 443 412 420 398 427 292 TD 449 388 353 363 428 252 Elongation
(%) MD 628 613 568 630 642 288 TD 628 625 635 613 724 508 Phosphorus strength
(g / 탆) MD 8.1 7.0 6.5 7.0 3.6 7.0 TD 20.1 15.4 17.2 14.2 6.3 5.9

Referring to the above Tables 2 and 3, the mLLDPE of Comparative Example 1 which is conventionally used commercially has good transparency, but has poor processability due to a narrow molecular weight distribution. In the case of LDPE of Comparative Example 2, transparency and workability are comparatively excellent, but mechanical properties such as impact strength and tensile strength are poor.

On the other hand, the olefin polymer prepared using the catalyst of the present invention exhibited good physical properties such as transparency, processability, and mechanical properties. In particular, in Examples 5 and 6 using three kinds of metallocene catalysts of different kinds, a broad molecular weight distribution and an MFRR were shown, and the processability was improved, and mechanical properties and transparency were also good, It is understood that the material properties are achieved at the same time.

Claims (8)

A first metallocene compound represented by Formula 1 below;
A second metallocene compound comprising a compound represented by Formula 2 and Formula 3;
A cocatalyst compound; And
Composite supported metallocene catalyst comprising a carrier:
[Chemical Formula 1]

In Formula 1,
R 1 to R 4, R 9 and R 1 'to R 4' are the same or different and each independently represents hydrogen, halogen, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 6 to C 20 aryl group, An aryl group, or an arylalkyl group of C7 to C20;
R5 to R8 are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group And at least two adjacent ones of R5 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring;
L1 is a linear or branched alkylene group of C1 to C10;
Wherein D1 is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, C2 to C20 alkenyl group, or C6 to C20 aryl group;
A 1 represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, An alkoxyalkyl group of C20, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
M1 is a Group 4 transition metal;
X1 and X2 are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, To C20 alkoxy groups, or C1 to C20 sulfonate groups;
(2)

In Formula 2,
R10 to R13 and R10 'to R13' are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, Or an aryl group of C1 to C20 or an amine group of C1 to C20, and at least two of R10 to R13 and R10 'to R13' are connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring Can be;
Z1 and Z2 are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C6 to C10 aryloxy group, A C2 to C20 alkenyl group, a C7 to C40 alkylaryl group, or a C7 to C40 arylalkyl group;
Q is a C1 to C20 alkylene group, a C3 to C20 cycloalkylene group, a C6 to C20 arylene group, a C7 to C40 alkylarylene group, or a C7 to C40 arylalkylene group;
M2 is a Group 4 transition metal;
X3 and X4 are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, To C20 alkoxy groups, or C1 to C20 sulfonate groups;
(3)

In Formula 3,
M3 is a Group 4 transition metal;
X5 and X6 are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, To C20 alkoxy groups, or C1 to C20 sulfonate groups;
R14 to R19 are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, C20 alkylsilyl, C6-C20 arylsilyl or C1-C20 amine group, and two or more adjacent R14 through R17 are connected to each other to form one or more aliphatic rings , An aromatic ring, or a heterocyclic ring;
L2 is a straight or branched alkylene group of C1 to C10;
D2 is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, C2 to C20 alkenyl group, or C6 to C20 aryl group;
A halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, An alkoxyalkyl group of C20, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
B is carbon, silicon, or germanium and is a bridge that covalently bonds the cyclopentadienyl ligand and JR 19 _zy ;
J is a Group 15 element or a Group 16 element of the periodic table;
z is the oxidation number of the element J;
y is the combined number of J elements.
2. A compound according to claim 1, wherein L 1 in the general formula (1) is a linear or branched alkylene group having from 4 to 8 carbon atoms and A 1 is hydrogen, methyl, ethyl, propyl, isopropyl, Propylmethyl group, a tert-butoxymethyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.
2. A compound according to claim 1, wherein Q in the formula (2) is an alkylene group of C1 to C20, Z1 and Z2 are each independently hydrogen, C1 to C20 alkyl or C1 to C20 alkoxy, Supported metallocene catalysts.
2. A compound according to claim 1, wherein L2 in the general formula (3) is a C4 to C8 linear or branched alkylene group, A2 is hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, Propylmethyl group, a tert-butoxymethyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.
The hybrid supported metallocene catalyst according to claim 1, wherein B in the general formula (3) is silicon and J is nitrogen.
delete The mixed catalyst according to claim 1, wherein the co-catalyst compound comprises at least one compound represented by the following general formula (4), (5) or (6)
[Chemical Formula 4]
- [Al (R20) -O] _n -
In Formula 4,
R20 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
[Chemical Formula 5]
D (R20) ₃
In Formula 5,
R20 is as defined in Formula 4 above;
D is aluminum or boron;
[Chemical Formula 6]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 6,
L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same or different from each other and each independently represents a C6 to C20 aryl group or a C1 to C20 alkyl group in which at least one hydrogen atom is substituted with halogen, C1 to C20 hydrocarbon, alkoxy or phenoxy.
A method for producing an olefin-based polymer, which comprises polymerizing an olefin-based monomer in the presence of the hybrid supported metallocene catalyst of any one of claims 1 to 5 and 7.